TW201623258A - Volatile dihydropyrazinly and dihydropyrazine metal complexes - Google Patents

Abstract

A composition comprising dihydropyrazinyl anions that can be coordinated as 6 electron ligands to a broad range of different metals to yield volatile metal complexes for ALD and CVD depositions are described herein. Also described herein are undeprotonated dihydropyrazines that can coordinate to metals as stabilizing neutral ligands. In one embodiment, the composition is used for the direct liquid injection delivery of the metal dihydropyrazinyl complex precursor to the chamber of an ALD or CVD chamber for the deposition of metal-containing thin films such as, for example, ruthenium or cobalt metal films.

Description

Volatile dihydropyrazinyl and dihydropyrazine metal complexes Cross-reference to related applications

The case is filed in the US Provisional Application No. 61/858,799, filed on July 26, 2013. The disclosure of this provisional application is incorporated herein in its entirety by reference.

Described herein are dihydropyrazine ligands which, for example, are used to synthesize metal complexes such as, but not limited to, ruthenium and cobalt complexes used in ALD or CVD precursors. Also included herein are complexes comprising a dihydropyrazine ligand and methods of making or using same.

The electronics industry is constantly looking for volatile metal-containing precursors for vapor deposition processes, including chemical vapor deposition (CVD) and atomic layer deposition (ALD), for use with these metal-containing precursors. The conformal metal-containing film is assembled on the following substrates, such as tantalum, metal nitrides, metal oxides, and other metal-containing layers. In these techniques, a vapor of a volatile metal complex is introduced into a process chamber to contact a surface of a crucible wafer, and a chemical reaction occurs on the surface of the crucible to deposit a thin film of a pure metal or metal compound. If the precursor CVD occurs by heating or by simultaneously adding reagents to the process chamber to react on the surface of the wafer and film growth occurs in a steady state deposition manner. The CVD can be supplied in a continuous or pulsed mode to achieve the desired film thickness. In ALD, the precursor is chemically adsorbed onto the wafer to become a self-saturating monolayer, and excess unreacted precursor is washed away with an inert gas such as argon, followed by addition of excess reagent, which is The chemisorbed precursor monolayer reacts to form a metal or metal compound. The excess reagent is then washed off with an inert gas. This cycle can then be repeated multiple times to accumulate the metal or metal compound to the desired thickness with atomic accuracy because the chemisorption of the precursor and reagent is self-limiting. ALD provides ultra-thin but still continuous inclusions by precise control of film thickness, excellent uniformity of film thickness, and significantly conformal film growth to uniformly coat deeply etched and highly crimped structures such as interconnect vias and trenches. Metal film. Suitable metal precursors for ALD include those that are thermally stable to exclude any thermal decomposition that occurs during the chemisorption stage but are still chemically reactive to the added reagents. In addition, these metal precursor monomers are important for clean vaporization with maximum volatility and leaving only a small amount of non-volatile residue. It is also desirable for such precursors to have high solubility in a hydrocarbon solvent to form a solution that can be used in direct liquid injection (DLI) to transport precursor vapors to the CVD or ALD reactor. Hydrocarbon solvents such as cyclooctane and mesitylene are particularly attractive because they are higher boiling liquids and can be easily dried to low humidity levels.

Niobium and cobalt are metals that are particularly attractive for CVD and ALD processes in semiconductor devices. The deposition of the ultra-thin film can be used to create electrodes in DRAM capacitor cells or to provide copper adhesion that promotes film growth on copper diffusion barrier materials such as titanium nitride or tantalum nitride. Ultra-thin continuous diaphragm can also be used as copper and gold The genus can be directly electroplated on the above seed layer. Similarly, the thin cobalt layer can also be used as a adhesion promoting film for titanium nitride or tantalum nitride. Alternatively, cobalt can be deposited as a 'cover film' on the copper interconnect. When either of the metals is deposited on titanium nitride, tantalum nitride or other substrate that may be reactive with elemental oxygen, it is particularly desirable that the ruthenium and cobalt complexes do not contain elemental oxygen as this will tend to form Metal oxides that can cause electrical failure within the device being assembled.

Many ruthenium precursors are described in the chemical literature, but the common process challenges encountered when using them in ALD are the long incubation times for forming continuous metal films and the necessity to use oxygen or ozone as reagents. Long incubation times are the result of low metal atomic deposition (nucleation) density in the earliest ALD cycles, as those sites where the core tends to act as further metal deposits cause the density to slowly increase with further cycling. The relationship between the ALD film thickness and the number of ALD cycles is established using the established sufficient nucleation density. In this way, it may be necessary to have 500 initial ALD cycles to establish a stable growth rate of the ruthenium membrane (S. Yim et al, Journal of Applied Physics, 103, 113509, 2008). The nucleation density can be enhanced by the application of plasma during the ALD process, but the strong orientation vectorization of the plasma tends to reduce the uniformity of deposition compared to thermal ALD, especially on the vertical side of the deep etched structure, which may be because The plasma is 'shadowed'. On the other hand, the use of oxygen and ozone agents may cause their ability to oxidize barrier films such as titanium nitride and tantalum nitride to be a problem and also cause roughening and etching of the base metal. In view of this, it is highly desirable to develop a ruthenium precursor capable of depositing ruthenium metal by a chemical reduction process, thereby avoiding oxidative damage. Suitable reagents for reduction include, but are not limited to, hydrogen, ammonia, amines, hydrazines, decanes, alanes, and boranes. The most needed process includes no one of them containing elemental oxygen. a combination of a flooding agent and a reducing agent. Similarly, there is a need for a method of reducing the growth of a cobalt metal film from an oxygen-free cobalt precursor under reducing conditions. Therefore, in general, it is necessary to use an oxygen-free ruthenium and cobalt precursor capable of depositing metal ruthenium and cobalt.

Other metal precursors described in the prior art include, but are not limited to, one or more of the following: cyclopentadienyl (Cp), pyrrole, imidazole, diene, CO, alkyl substituted phenyl, fluorenyl, A thiol group or a combination thereof. However, the ligands and complexes described herein differ from those of the prior art in that they are based on non-aromatic dihydropyrazine ligands that enable them to grow with high reactivity by ALD and CVD. Metal film and no oxygen.

Described herein are hydropyridine-containing metal-containing complexes having Formulas 3A through 3E as described herein. In certain embodiments, the metal M is selected from the group consisting of Ru or Co. In some embodiments, the complexes may be used, for example, for direct liquid injection (DLI) of ALD and CVD processes. These complexes can additionally contain one or more solvents, such as hydrocarbons or other solvents, and can be enclosed or stored in stainless steel containers.

N-alkyl dihydropyrazines and N-trialkyldecyl dihydropyrazines are also described herein.

Also described herein are ALD and CVD deposition processes in which the hydropyridine-containing metal complexes, more specifically, the complexes containing ruthenium and cobalt, and a reducing agent selected from hydrogen, are used in the deposition process. , ammonia, hydrazines, decanes, boranes.

Also described herein are ALD and CVD deposition processes that use such A complex containing a hydrogen pyrazine metal, more specifically a complex containing ruthenium and cobalt, with an oxidizing agent such as ozone or oxygen.

Described herein are compositions comprising a metal dihydropyrazinyl complex that can be used to transport these precursors DLI to a vapor deposition process such as atomic layer deposition (ALD) and chemical vapor deposition of metal containing films. (CVD) growth method. In order to transport these precursors via DLI, these precursor physics should also be readily soluble at high enough concentrations to form compositions suitable for DLI transport. The compositions of the metal dihydropyrazinyl complexes described herein exhibit both volatility and thermal stability under vaporization conditions. In addition, it can be used very efficiently as a precursor to any other application of metal film growth and a volatile source that requires a metal precursor.

In yet another aspect, there is provided a method for forming a metal oxide film on a substrate, wherein the film comprises a thickness, the method comprising: a. introducing from the formula 3A, 3B, 3C, 3D, 3E a metal dihydropyrazinyl complex of 3F, 3G and 3H complex or a combination thereof; b. chemically adsorbing the metal dihydropyrazine based complex on the substrate; c. using a wash The net gas washes off the metal dihydropyrazinyl complex; d. provides a source of oxygen to the metal dihydropyrazinyl complex on the heated substrate to react with the adsorbed metal dihydropyrazine The base complex reaction; and e. optionally wash away any unreacted oxygen source, wherein steps a through d are repeated until the desired film thickness is obtained.

Figure 1 is (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl -Structural diagram of -5,6-diethylpyrazinyl)anthracene.

Figure 2 provides the heat of (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)anthracene (Ru(Cp)DMDEP) Weight analysis (TGA) / differential scanning calorimetry (DSC) results.

Figure 3 is a structural diagram of (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine) cobalt.

Figure 4 provides TGA/DSC results for (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)cobalt.

Figure 5 is a structural diagram of potassium (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)(tetrahydrofuran).

Figure 6 is an X-ray photoelectron spectroscopy [XPS] of a ruthenium atomic layer deposited on TiO ₂ using RuCp*DMDEP/oxygen at 300 °C.

Described herein are compositions comprising a dihydropyrazinyl anion capable of producing a volatile metal for ALD and CVD deposition when a 6-electron ligand is coordinated to a wide variety of different metals. Compound. In certain embodiments, the highly hindered substituted dihydropyrazinyl anion is suitable for use in complexes comprising earth metals. In other embodiments, the dihydropyrazinyl group substituted with a lower steric hindrance is suitable for a complex comprising a further transition metal and a lanthanum metal. In still other embodiments, neutral undeprotonated dihydropyrazine can be used, for example, as a 4-electron donor ligand. With respect to the following specific examples, the zero valent oxime complex can be made from the 18 electron complex of dihydropyrazine (4 electrons), ruthenium (0) (8 electrons), and toluene (6 electrons). An advantage of the dihydropyrazine ligand described herein is that it may be reactive with water or hydroxyl groups (OH) due to hydrogen bonding to the ring nitrogen, resulting in a metal or metal oxide film after hydrolysis/breaking of the ring. Deposition. Without being bound by theory, this reactivity should be higher compared to a similar complex with a non-hydrolyzed, unstable cyclohexadiene ligand. In yet another embodiment, the neutral and deprotonated dihydropyrazines can be used in combination with other ligands, such as cyclopentadiene (Cp), pyrrole, imidazole, sulfhydryl, decyl, diimine. A ketimine or a diketone or the like to form a mixed ligand complex. The resulting composition or complex comprising a dihydropyrazine ligand disclosed herein enables it to simultaneously serve as a deposition process, more specifically the volatility required for the atomic layer deposition process, and can be maintained under vaporization conditions. Thermal stability. In addition to the foregoing, such compounds or complexes and compositions comprising such compounds or complexes can be used in the growth of metal films, such as, but not limited to, tantalum or cobalt metal films, and require the volatilization of metal precursors. Any other application of sexual origin.

The metal dihydropyrazinyl complex described herein contains one or more metals selected from Groups 2 to 16 or Groups 4 to 16. In certain embodiments of the formulas described herein, M is selected from the group consisting of metals of Groups 4 to 16, including, but not limited to, Fe, Co, Ni, Cr, Mn, Ru, Rh, Pd, Os, Ir , Pt, Cu, Zn, In, Ge, Sn, Sb, Te, Bi, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Al, In, Sn, Sb, Bi; La, Ce , Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and combinations thereof. In a specific embodiment, the M is Ru. In another specific embodiment, the M is Co.

Described herein is a method for synthesizing a metal dihydropyrazine based complex, such as, but not limited to, an oxygen-free oxime based on a dihydropyrazine ligand. And cobalt precursors. These novel compounds are haplotypes, are clean and volatile, and have high solubility in hydrocarbon solvents. The dihydropyrazine ligands can be added in their deprotonated form as dihydropyrazinyl anions, as dihydropyrazinyl radical anions or as neutral (unprotonated) ligands. Complex compound. These different coordination sub-configurations are shown in Equation 1.

In addition, N-alkyldihydropyrazines or N-trialkyldecyldihydropyrazines can also be used as neutral molecules or as N-alkyldihydropyrazinyl or N-trialkyl groups. The decyl dihydropyrazinyl radical anions are added to the novel complexes. These ligand configurations are shown in Formula 2 for N-trialkyldecyl dihydropyrazine.

The metal dihydropyrazinyl complex can form more than one dihydropyrazinyl anion, or more than one dihydropyrazinyl radical anion, or more than one N-alkyl dihydropyrazinyl free Base anion, or more than one N- Trialkyl decyl dihydropyrazinyl radical anion.

In another embodiment, the complex is capable of forming a single dihydropyrazinyl anion, or a single dihydropyrazinyl radical anion, or the only one N-alkyldihydropyrazinyl radical anion Or the only one trialkylsulfonyl dihydropyrazinyl radical anion combined with other different anions such as pentamethylcyclopentadienyl. These complexes are shown in formulas lines 3A, 3B. 3C and, wherein ^{R 1, R 2, R 3} , R 4 are each independently selected from the Department of C ₁ -C ₆ linear, branched or cyclic alkyl group; R ⁵ is independently Department Is selected from a hydrogen atom or a linear, branched or cyclic C ₁ -C ₆ alkyl group; R ⁶ is independently selected from a C ₁ -C ₃ linear or branched alkyl group; (L) is an anion selected from the group consisting of cyclopentane Dienyl, pentamethylpentadienyl, dimethylpentadienyl, trimethylpentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl, imidazolyl, trialkyl Imidazolyl, pyrrolyl, alkylpyrrolyl; M-based divalent metal; x = 1 or 2; x + y = 2; and X in the formula 3C is independently selected from a hydrogen atom, C ₁ - C ₆ linear, Branched or cyclic alkyl and SiR ⁶ , and wherein R ⁶ is independently selected from C ₁ -C ₃ linear or branched alkyl.

In yet another embodiment, the above formulas 3A, 3B, and 3C can comprise M, which may have a "+1" oxidation state or a monovalent metal. In these embodiments, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and (Q) are neutral ligands such as, but not limited to, benzene or alkylated benzene described herein. When x is 1; y becomes 0 (for example, L does not exist); and the new variable 'z' is 1. A general example of Formulas 3A, 3B, and 3C, in which the M system unit price may be as follows: (anion) _x M ^{+ n} (L) _y (Q) _z . More specific examples of these compounds are represented by the following formulas 3F, 3G and 3H.

The complex can also be formed to contain a neutral (unprotonated) dihydropyrazine of the formula 3D wherein R ¹ , R ² , R ³ , R ⁴ are each independently selected from C ₁ a -C ₆ linear, branched or cyclic alkyl group; R ⁵ is independently selected from a hydrogen atom and a C ₁ -C ₆ linear, branched or cyclic alkyl group; (L) is an anion selected from the group consisting of cyclopentadiene , pentaalkylcyclopentadienyl, pentamethylpentadienyl, dimethylpentadienyl, trimethylpentadienyl, methylcyclopentadienyl, ethylcyclopentadienyl , imidazolyl, trialkylimidazolyl, pyrrolyl and alkylpyrrolyl; M monovalent metal; x = 1 or 2; y = 1; and Z is independently selected from hydrogen atoms, C ₁ -C ₆ linear, Branched or cyclic alkyl and SiR ⁶ wherein R ⁶ is independently selected from linear, branched or cyclic C ₁ -C ₃ alkyl.

The complex can also be formed to contain a neutral (unprotonated) dihydropyrazine of the formula 3E wherein R ¹ , R ² , R ³ , R ⁴ are each independently selected from C ₁ -C ₆ linear, branched or cyclic alkyl; R ⁵ is a hydrogen atom or a C ₁ -C ₆ linear, branched or cyclic alkyl group; (Q) is a benzene or alkylated benzene; M is in the 0 oxidation state a metal; x = 1 or 2; y = 1; and the Z series is independently selected from a hydrogen atom or a C ₁ -C ₆ linear, branched or cyclic alkyl group and SiR ⁶ wherein R ⁶ is linear, branched or cyclic C _1- C ₃ alkyl.

In the above formulas 3A, 3B, 3C and 3D, (L) may also be a dihydropyrazine anion, a dihydropyrazine radical anion, an N-alkyl dihydropyridyl which is different from the (dihydropyrazine) x. a azine radical anion, an N-trialkylsulfanyl dihydropyrazine radical anion.

It is shown that the dihydropyrazinyl anion of this disclosure is coordinated to the oxime in the η-5 mode, as shown in (1) with respect to (pentamethylcyclopentadienyl) (2,2-dihydro-3,3). -Illustration of dimethyl-5,6-diethylpyrazinyl), wherein Ru1 is bonded to C1, N1, C6, C3 and N2 of the DMDEP ligand. In this manner, the DMDEP anion acts as a 6-electron donor, wherein the formal 2 electrons are provided by the anion negative charge, and then the two double bonds of the ligand each provide another 2 electrons. In this manner, the dihydropyrazinyl anions can assist in providing an 18-electron coordination sphere around the transition metal to provide a stable complex. Thus, in the case of (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)anthracene, 6(d) electron It is provided by Ru ^{+ 2} , 6 from the dihydropyrazinyl anion and 6 electrons from the pentamethylcyclopentadienyl anion to give a total of 18 electrons. Neutral (unprotonated) dihydropyrazine ligand, N-alkyldihydropyrazine or trialkyldecyl dihydropyrazine can be coordinated to the metal in a similar η-4 mode As a 4 electron donor, 2 electrons are each provided by the two double bonds of the ligands. Referring now to Figure 3 or the structure of (pentamethylcyclopentadienyl)(2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)cobalt, 8(d) electron It is provided by Co ⁺¹ , 6 electrons are supplied from the pentamethylcyclopentadienyl anion and 4 electrons are supplied from the dihydropyrazine ligand to obtain a total of 18 electrons. N-alkyl dihydropyrazines and N-trimethyl decyl alkyl dihydropyrazines can form N-alkyl dihydropyrazinyl and N-trimethyl decyl alkyl groups by one-electron reduction, respectively. a hydropyrazinyl radical anion such that its negative charge is displaced across the 4 atom of the dihydropyrazine ring and is capable of supplying 2 electrons from a formal negative charge, 2 from the double bond and 1 electron from the reducing external electron To get a total of 5 electrons. These radical anion configurations are also shown in the above formula 2 as N-trimethylalkylalkyldihydropyrazines.

Although not wishing to be bound by theory, since the dihydropyrazine ligands and their anions are non-aromatic, their reduction by hydrogen to their corresponding amines is not hindered by the loss of aromatic stabilization and the reduction is Provided by 钌 Or other metals are catalyzed. Once the dihydropyrazine ligand is reduced, it can no longer supply the metal stabilization, which is then reduced to its metallic state.

Notable morphologies of the complexes of this disclosure are based on the chemical literature (D. Gopal et al., Tetrahedron Letters, 39, 1877-1880, 1998) ("Gopal et al."), of the type described herein or The alkyl-substituted dihydropyrazine of the quaternary carbon of the dialkyl substituted position 3 undergoes exoprotonation to produce a thermolabile anion whose negative charge cannot be displaced around the dihydropyrazinyl ring, such as The following formula 4 is illustrated. In contrast, Applicants have shown herein that the deprotonation of the in-ring ligands of alkyl-substituted dihydropyrazines can be readily achieved to produce a shift of 5 atoms across their dihydropyrazinyl ring. Anions, as illustrated in Formula 5, and additionally produced anions are thermally stable. The Gopal et al. reference also states that dimerization of the dihydropyrazine occurs after storage at -15 °C. However, Applicants have found that 2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine is stable at room temperature. Furthermore, the hydrazine and cobalt complexes based on the dihydropyrazines described herein are also stable. By separating potassium (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)(tetrahydrofuran) into a crystalline solid at room temperature and crystallizing by X-ray It is proved that it is in the η-5 mode of potassium (+1). As shown in Figure 5, the applicant also found (2,2-dihydro-3,3-dimethyl-5,6-diethyl Potassium pyridazine) (tetrahydrofuran) is thermally stable. In summary, the thermal stability of the dihydropyrazines described herein and their in-ring deprotonation provide a stable and fully displaced anion from which a stable and volatile metal complex can be prepared. In addition, described herein are N-alkyl dihydropyrazines and N-trialkyldecyl dihydropyrazines, which are believed to provide stability and volatilization. Sexual metal complex.

The metal dihydropyrazine based complexes or compositions described herein are well suited for use in the fabrication of semiconductor type microelectronic devices, such as microcapacitor cells for memory applications such as DRAM devices, ALD, CVD, pulsed CVD, electricity. Volatile precursors for slurry reinforced ALD (PEALD) or plasma enhanced CVD (PECVD). These complexes are also very useful for the manufacture of pyrodetector devices. The method used to form the metal-containing films or coatings is a deposition process. Examples of suitable deposition processes for the methods disclosed herein include, but are not limited to, cyclic CVD (CCVD), MOCVD (metal organic) CVD), thermal chemical vapor deposition, plasma enhanced chemical vapor deposition ("PECVD"), high density PECVD, photon assisted CVD, plasma-photon assisted ("PPECVD"), low temperature chemical vapor deposition, chemically assisted gas Phase deposition, hot wire chemical vapor deposition, CVD of liquid polymer precursors, supercritical fluid deposition and low energy CVD (LECVD). In some embodiments, the metal-containing film is deposited via an atomic layer deposition (ALD), plasma enhanced ALD (PEALD), or plasma enhanced cyclic CVD (PECCVD) process. As used herein, the phrase "chemical vapor deposition process" means any process for exposing a substrate to one or more volatile precursors that react and/or decompose on the substrate to produce desired Deposition. As used herein, the phrase "atomic layer deposition process" means the continuous surface chemistry of depositing a film of material onto a substrate of varying composition (eg, the amount of film material deposited during each reaction cycle is fixed). Although the precursors and sources used herein may sometimes be described as "gaseous," it is understood that the precursors may be liquid or solid, either by direct vaporization, foaming or sublimation, or by inert gas. Inside the reactor. In some cases, the vaporized precursors can pass through a plasma generator. In a specific embodiment, the metal-containing film is deposited using an ALD process. In another embodiment, the metal-containing film is deposited using a CCVD process. In another embodiment, the metal-containing film is deposited using a thermal CVD process. The phrase "reactor" as used herein includes, but is not limited to, a reaction chamber or a deposition chamber.

In some embodiments, the methods disclosed herein utilize ALD or CCVD methods to avoid pre-reaction of the metal precursors, which separate the precursors before and/or during introduction to the reactor. About this The dielectric film is deposited using a deposition technique such as an ALD or CCVD process. In one embodiment, the film is exposed to the one or more metal dihydropyrazinyl complex compositions, oxygen source, reducing agent, and/or other via an ALD process by alternately exposing the substrate surface to the one or more metal dihydropyrazine-based complex compositions. Precursors or reagents are deposited. The film growth is carried out by the self-limiting control of the surface reaction, the pulse length of each precursor or reagent, and the deposition temperature. However, once the surface of the substrate is saturated, the film growth stops.

According to the deposition method, in some embodiments, the one or more metal dihydropyrazinyl complexes may be introduced into the reactor at a predetermined molar volume or from about 0.1 to about 1000 micromoles. in. In various embodiments, the metal dihydropyrazinyl complex precursor can be introduced into the reactor for a predetermined period of time. In certain embodiments, the period is between about 0.001 and about 500 seconds.

In certain embodiments, the membranes deposited using the methods described herein are formed using an oxygen source, a reagent, or a precursor comprising oxygen in the presence of oxygen. The source of oxygen may be introduced into the reactor in at least one oxygen source form and/or may be incidental to other precursors used in the deposition process. Suitable oxygen source gases may include, for example, water (H ₂ O) (eg, deionized water, pure water, and/or distilled water), oxygen (O ₂ ), oxygen plasma, ozone (O ₃ ), NO. , N ₂ O, NO ₂ , carbon monoxide (CO), carbon dioxide (CO ₂ ), and combinations thereof. In certain embodiments, the source of oxygen comprises an oxygen source gas introduced into the reactor at a flow rate of from about 1 to about 2000 standard cubic centimeters (sccm) or from about 1 to about 1000 sccm. This source of oxygen may be introduced over a period of from about 0.1 to about 100 seconds. In a particular embodiment, the source of oxygen comprises water having a temperature of 10 ° C or higher. In a specific embodiment of depositing the film by an ALD or cyclic CVD process, the precursor pulse can have a pulse period greater than 0.01 seconds, and the source of oxygen can have a pulse period of less than 0.01 seconds during which the water pulse can Has a pulse period greater than 0.01 seconds. In yet another embodiment, the wash period between the pulses may be as short or continuous as 0 seconds without being washed therebetween.

In some embodiments, the process utilizes a reducing agent. The reducing agent is usually introduced in a gaseous state. Examples of suitable reducing agents include, but are not limited to, hydrogen, hydrogen plasma, remote hydrogen plasma, decane (i.e., diethyl decane, ethyl decane, dimethyl decane, phenyl decane, decane). , acetane, amino decane, chlorodecane, borane (ie, borane, diborane), alane, decane, hydrazine, ammonia or mixtures thereof.

The deposition methods disclosed herein may involve one or more purge gases. The cleaning gas is used to wash away unconsumed reactants and/or reaction by-products, and is an inert gas that does not react with the precursors. Exemplary cleaning gases include, but are not limited to, argon (Ar), nitrogen (N ₂ ), helium (He), helium, hydrogen (H ₂ ), and mixtures thereof. In certain embodiments, a purge gas, such as an Ar system, is supplied to the reactor at a flow rate of from about 10 to about 2000 sccm for about 0.1 to 1000 seconds to wash unreacted materials and any possible residues. By-product in the reactor.

The individual steps of supplying such precursors, oxygen sources and/or other precursors, source gases and/or reagents can be carried out by varying the stoichiometric composition of the resulting membranes by varying the supply.

Applying energy to the precursor, source of oxygen, reducing agent, At least one of his precursors or combinations thereof initiates a reaction and forms the metal-containing film or coating on the substrate. This energy may be via, but not limited to, heat, plasma, pulsed plasma, helicon plasma, high density plasma, induced coupling plasma, X-ray, electron beam, photon, remote plasma method And its combination to provide. In some embodiments, a secondary radio frequency (RF) frequency source can be used to alter the plasma characteristics of the substrate surface. In a specific embodiment where the deposition involves plasma, the plasma generation process may comprise a direct plasma generation process in which the plasma is produced directly in the reactor, or selectively produces plasma on the outside of the reactor and is supplied to the plasma. The remote plasma within the reactor produces a process.

The metal dihydropyrazinyl complex precursors can be delivered to the reaction chamber, such as a CVD or ALD reactor, in a variable manner. In a specific embodiment, a liquid delivery system can be utilized. In an alternative embodiment, a combined liquid delivery and flash vaporization processing unit can be utilized, such as, for example, a turbine vaporizer manufactured by MSP Corporation of Huelva, Minnesota. Low volatility materials can be delivered in a volumetric flow mode resulting in reproducible transport and deposition without thermal decomposition of the precursor. The precursor compositions described herein can be effectively used as source reagents in a DLI mode to feed vapor streams of these metal dihydropyrazinyl complex precursors into an ALD or CVD reactor.

In certain embodiments, these compositions include those utilizing hydrocarbon solvents that are particularly suitable due to their ability to be dried to levels below the ppm level. Exemplary hydrocarbon solvents that can be used in the present invention include, but are not limited to, toluene, mesitylene, cumene (isopropylbenzene), p-cumene (4-isopropyltoluene), 1,3-diiso Propylbenzene, octane, dodecane, 1,2,4-trimethylcyclohexane, n-butyl Cyclohexane and decalin (decahydroquinone). The precursor composition of the present invention may also be stored in a stainless steel container and used in a stainless steel container. In certain embodiments, the hydrocarbon solvent in the composition is a high boiling solvent or has a boiling point of 100 ° C or higher. The group of metal dihydropyrazinyl complex precursor compositions of the present invention may also be mixed with other suitable metal precursors, and the mixture is used to simultaneously transport two metals for growth of binary metal oxides or nitrides. membrane.

In some embodiments, the purity of the precursor compositions is high enough to be acceptable for reliable semiconductor fabrication. In certain embodiments, the metal-containing precursors described herein and compositions comprising the same comprise less than 2% by weight, or less than 1% by weight, or less than 0.5% by weight of one or more of the following impurities: Free amines, free halides or halides, and higher molecular weight species. The higher purity of the metal dihydropyrazinyl complex precursors described herein can be obtained by one or more of the following processes: purification, adsorption, and/or distillation.

In some embodiments, the gas lines connecting the precursor cartridges to the reaction chamber are heated to one or more temperatures and the vessel containing the composition is maintained at one or more temperatures depending on the requirements of the process. For blistering. In other embodiments, a composition comprising the metal dihydropyrazinyl complex precursor is injected into a vaporizer maintained at one or more temperatures for direct liquid injection.

Argon and/or other gas streams may be employed as a carrier gas to assist in transporting vapors of the at least one family of metal dihydropyrazinyl complex precursors to the reaction chamber during the pulse of the precursor. In some embodiments, the reaction chamber process pressure is about 1 Torr.

In a typical ALD or CCVD process, initially exposed to A substrate such as a ruthenium oxide substrate is heated on the heater section of the reaction chamber of the metal dihydropyrazinyl complex precursor to enable chemical adsorption of the complex on the surface of the substrate.

A purge gas, such as argon, washes away excess complexes that are not adsorbed from the processing chamber. After sufficient washing, a nitrogen-containing source can be introduced into the reaction chamber to react with the adsorbed surface, followed by another gas wash to remove reaction by-products from the chamber. This process cycle can be repeated to achieve the desired film thickness.

In various embodiments, the steps of the methods described herein can be performed in a variable order, either continuously or simultaneously (eg, during at least a portion of another step), and any combination thereof. get on. The individual steps of supplying the precursors and the nitrogen-containing source gases can vary the stoichiometric composition of the resulting dielectric film by varying the period during which they are supplied.

In another embodiment of the method disclosed herein, the metal or metal oxide film is formed using an ALD deposition process comprising the steps of: providing a substrate in a reactor; comprising comprising a moiety selected from Formula 3A, 3B a composition of a metal dihydropyrazinyl complex of a 3C, 3D, 3E compound or a combination thereof, introduced into the reactor; chemically adsorbing the precursor of the metal-containing dihydropyrazinyl complex On the substrate; washing off the unreacted metal-containing dihydropyrazinyl-based precursor precursor using a purge gas; supplying a source of oxygen to the metal-containing dihydropyrazinyl group on the heated substrate Precursor of the complex with at least one metal-containing dihydropyrazinyl group adsorbed Precursor reaction of the complex; and optionally washing off unreacted sources of oxygen.

In still another embodiment of the method disclosed herein, the metal film is formed on the substrate by an ALD deposition method, wherein the film comprises a thickness, the method comprising: a. introducing at least one selected from the group consisting of Formula 3A, a metal dihydropyrazinyl complex of 3B, 3C, 3D compound or a combination thereof; b. chemically adsorbing the metal dihydropyrazine based complex on the substrate; c. washing with a purge gas Removing the metal dihydropyrazinyl complex; d. optionally providing a reducing agent to the metal dihydropyrazinyl complex on the heated substrate to react with the adsorbed metal dihydropyrazinyl group a complex reaction; and e. optionally washing off any unreacted reducing agent, and wherein the reducing agent can be selected from the group consisting of hydrogen, hydrogen plasma, ammonia, ammonia plasma, hydrogen/nitrogen plasma, alkyl decane and The mixture and in which steps a to e are repeated until the thickness of the metal film is obtained.

The above steps define a period of one of the methods described herein; and this period can be repeated until the desired film thickness is obtained. In various embodiments, the steps of the methods described herein may be performed in a plurality of different orders, and may be performed continuously or simultaneously (eg, during at least a portion of another step), and any Combined. The individual steps of supplying the precursors and oxygen sources can be varied by supplying a period of time to change the stoichiometric composition of the resulting dielectric film, but always using oxygen below the stoichiometric amount relative to the available enthalpy .

With regard to multi-component membranes, other precursors such as ruthenium-containing precursors, nitrogen-containing precursors, reducing agents, or other reagents can be introduced into the reaction chamber in turn.

In another embodiment of the method disclosed herein, the dielectric film is deposited using a thermal CVD process. In this particular embodiment, the method comprises: placing one or more substrates in a reactor heated to a temperature between ambient temperature to about 700 ° C and maintained at a pressure of 1 Torr or less; Introducing a composition comprising the metal dihydropyrazinyl complex, the metal dihydropyrazine based complex comprising at least one selected from the group consisting of Formula 3A, 3B, 3C, 3D compounds or combinations thereof; A source is supplied to the reactor to at least partially react with the metal dihydropyrazinyl complex and a metal film is deposited on the one or more substrates. In some embodiments of the CVD process, the reactor is maintained at a pressure of between 100 mTorr and 600 mTorr during the introduction step.

The above steps define one of the cycles associated with the methods described herein; and the cycle can be repeated until the desired film thickness is obtained. In various embodiments, the steps of the methods described herein can be performed in a variable sequence, either continuously or simultaneously (eg, during at least a portion of another step), and any combination thereof. . The individual steps of supplying the precursors and oxygen source gases can be varied by varying the stoichiometric composition of the resulting membrane.

With regard to multi-component membranes, other precursors such as ruthenium-containing precursors, nitrogen-containing precursors, oxygen sources, reducing agents, and/or other reagents can be introduced into the reaction chamber in turn.

Described herein is a method of depositing a metal-containing film by ALD or CVD, the method comprising using the composition of the present invention comprising a metal dihydropyrazinyl complex precursor as described above. In a specific embodiment, a method of depositing a metal-containing film is provided by delivering a composition comprising the metal dihydropyrazinyl complex precursor and a compatible solvent to the reaction by DLI transport. a chamber, which is then reacted with an oxygen source to grow a metal-containing film selected from the group consisting of water, alcohol, oxygen, ozone, nitrogen monoxide, nitrogen dioxide, hydrogen peroxide, or combinations thereof, The process employs a reactor pressure of from about 0.001 to about 1000 Torr and a temperature of from 0 to 1000 °C. Depending on the identification of the metal, this method results in the deposition of a metal oxide of about 1 angstrom (Å) per cycle.

The invention is also a method of growing a dielectric or metal film using one or more metal dihydropyrazine based complex precursors described herein to form a device selected from the group consisting of dynamic random access memory (DRAM) a microelectronic device of a group consisting of a memory cell and a pyrometric device.

Alternatively, the present invention is a method of fabricating a microelectronic device using the imidazole-based structure of the present invention, the microelectronic device being selected from the group consisting of: a non-volatile ferroelectric microelectronic memory device for electrophoresis A display phosphor of a light-emitting display, a high Tc superconducting device.

In still another embodiment, the invention is a method of growing a metal metal oxide or nitride film by ALD or CVD, comprising: providing a metal dihydropyrazinyl complex dissolved in a solvent, The solvent is selected from the group consisting of ethers, amine ethers, guanamines, esters, aromatic hydrocarbons or hydrocarbon solvents; and the resulting composition is delivered via a DLI system to provide a vapor stream of the resulting composition. The metal oxide or nitride film is grown by ALD or CVD.

Example Example 1: Synthesis of 2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine (for example, HDMDEP)

50.0 g (0.438 mol) of 3,4-hexanedione was dissolved in 250 ml (ml) of tetrahydrofuran (THF), and 38.6 g (0.438 mol) of H ₂ NC(Me) ₂ CH ₂ NH was added with stirring. _{2 After} 30 minutes, it was kept at 20 to 25 ° C by ice bath cooling. The mixture was then stirred overnight. The mixture was then stirred with 20 g (g) of anhydrous magnesium sulfate overnight, filtered and THF was evaporated in vacuo to give a yellow liquid (58 g). This was then placed on a 20 g dry moire for 2 days. The moire screens were then removed and the crude material was transferred by bottle to bottle at 65 C/100 mTorr and the final product was collected to a very pale yellow-green liquid. The product was produced in an amount of 47 g (65%). Gas Chromatography-Mass Spectrometry (GCMS) showed a parent ion of 166 mu.

Example 2: (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)anthracene (for example, RuCp*DMDEP) synthesis

Under a argon exhaust atmosphere, 9.3 g (0.056 mol) of HDMDEP dissolved in 20 ml of tetrahydrofuran was added dropwise to 10.66 g (0.053) in 200 ml of tetrahydrofuran cooled to -78 C over 10 minutes. Mohr) potassium hexamethyldioxane. The resulting mixture was stirred at -78 ° C for 30 minutes and then allowed to slowly warm to room temperature over 2 hours. The resulting KDMDEP solution was then subjected to a 14.25 g solution of chloro(pentamethylcyclopentadienyl)phosphonium (+2) tetramer which was stirred in a solution of 300 ml of tetrahydrofuran at room temperature for 20 minutes via a catheter (example) For example, RuCp*Cl) (0.052 molar 钌). The mixture was then refluxed for 2 days. The solvent was then removed by vacuum and 300 ml of hexane was added under argon. The resulting mixture was stirred for 20 minutes and then filtered to give a dark brown filtrate. The hexane was removed by vacuum to yield a dark brown tar. The tar was then subjected to bottle-to-bottle distillation at 140 ° C / 100 mTorr to produce a golden yellow liquid which solidified over a period of 2 days to give a crystalline agglomerate. The supernatant was transferred to a freezer at -20 ° C for 3 days to produce a second harvested crystal. The two batches of crystals were then combined and vacuum distilled at 140 ° C to discard the initial fraction, which was a minor excess of dihydropyrazine, and the major fraction was collected as a brownish brown oil which solidified into golden brown crystals over a period of 2 days. The production amount was 11.0 g (52%). The melting point of 54 ° C, TGA gave 2.08 wt% residue, as shown in Figure 2. X-ray crystallography confirmed that the structure was a monomeric type RuCp* (DMDEP).

¹ H NMR: (500MHz, D8 toluene): δ = 0.42 (s, 3H), δ = 1.14 (t, 3H), δ = 1.44 (s, 3H), δ = 1.45 (t, 3H), δ = 1.67 (s, 15H), δ = 2.4-2.5, 2.7-2.8 (m, 4H), δ = 3.67 (s, 1H). GCMS shows the parent ion at 401 mu.

Example 3: Synthesis of (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)cobalt (for example, CoCp*HDMDEP)

Under a nitrogen atmosphere, 0.68 g (0.005 mol) of pentamethylcyclopentadiene was added to 20 ml of THF containing 0.2 g (0.005 mol) of potassium hydride and the mixture was warmed under the action of nitrogen. After 2 hours to 45 C to produce a beige suspension. Then 0.65 g (0.005 mol) of cobalt dichloride was added and the mixture was stirred at room temperature overnight to give a dark brown mixture. 1.02 g (0.005 mol) of KDMDEP (THF) solid dissolved in 5 ml of THF was added and the mixture was stirred overnight. The THF was then removed by vacuum and the dark oily mass was extracted with 30 mL hexanes and filtered. The hexane was distilled off by vacuum and the dark brown oil was distilled from a bottle to bottle at 120 C/100 mTorr to give an initial reddish brown oil, followed by a very dark red crystalline product. Production = 0.4 g (22%), melting point 126.5 C, TGA residue 8.12% by weight, as shown in FIG. GCMS shows the parent ion out of 360mu. ¹ H NMR: (500MHz, D8 toluene): δ = 0.95 (s, 3H), δ = 0.97 (s, 3H), δ = 1.01 (t, 3H), δ = 1.42 (t, 3H), δ = 1.45 (m, 1H), δ = 1.71 (s, 15H), δ = 1.73 (m, 1H), δ = 2.20 (m, 1H), δ = 2.4 (m, 1H), δ = 3.29 (s, 1H) .

X-ray crystallography confirmed that the structure was a haplotype CoCp* (HDMDEP) in which Co1 was bonded to C12, N2, C13 and C14 of HDMDEP, that is, η-4 coordination.

Example 4: Synthesis of (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl)(tetrahydrofuran)potassium (for example, KDMDEP in THF)

Under an argon atmosphere, 5 ml of THF containing 1.7 g (0.01 mol) of HDMDEP was added to 30 ml of THF containing 1.8 g (0.0090 mol) of KHMDZ on dry ice for 2 minutes and stirred on dry ice for 90 minutes. It was then warmed to room temperature for 90 minutes. The solvent hexamethyldioxane and undeprotonated HDMDEP were removed under vacuum to produce a crude solid. The small sample was then suspended in boiling hexane and THF was added dropwise until the suspension dissolved. After cooling to room temperature, a small crystal is formed, which is shown to be the desired 2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine according to X-ray crystallography (Fig. 5). A base anion which is coordinated to potassium in the η-5 mode, wherein K1 is bonded to C9, N1, C12, C11 and N2. A THF molecule is also assigned to each potassium ion. For the NMR sample, all THF was pumped off and the sample was prepared in deuteron tetrahydrofuran. ¹ H NMR: (500MHz, D8 THF): δ = 0.78 (s, 6H), δ = 0.94 (t, 3H), δ = 1.04 (t, 3H), δ = 2.03 (q, 2H), δ = 2.31 (q, 2H), δ = 4.85 (s, 1H).

Example 5: Synthesis of (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)(phenyl)anthracene

5 ml of THF containing 1.33 g (0.006 mol) of HDMDEP was added to a solution of 1.6 g (0.0054 mol) of potassium hexamethyldioxane in 50 ml of THF at -78 C, followed by a 2 hour (hrs) warming. Change to room temperature. This solution was then added to 50 ml of THF containing 1.0 g (0.004 mol of Ru) of RuCl ₂ .benzene. The mixture was refluxed for 8 hours, then the solvent was removed under vacuum and the resulting mass was extracted with 100 ml of hexane and filtered. The hexane was removed under vacuum and the resulting brown oil was distilled from a bottle to bottle at 150 C/100 mTorr to give a brown brown oil distillate. GCMS showed a Ru(HDMEP) (benzene) parent ion from 346 mu.

Example 6: Using RuCp*DMDEP current precursors and oxygen as ALD conditions to deposit base metals under ALD conditions

The tantalum film was grown on a tantalum wafer coated with titanium oxide and titanium nitride using a CN-1 sprinkler head type ALD reactor under ALD conditions. The process cycle used was such that 50 sccm argon was washed at 138 C/600 sccm argon/100 sccm oxygen/600. Sccm argon was washed under RuCp*DMDEP using a cycle time of 5/20/5/20 seconds. 600 sccm argon wash containing 300 sccm of precursor pipe wash and 300 sccm of reagent pipe wash. The wafer temperature is 300C and the ALD compartment pressure is 3 Torr. This cycle was repeated 450 times to produce a Ru film of about 15 nm, the XPS analysis of which is shown in Figure 6. Secondary ion mass spectrometry (SIMS) analysis of the ruthenium film grown over 300 process cycles under the same conditions showed <1.0 atomic % carbon and oxygen levels.

The 9.3 nm (nm) tantalum film was also grown on a TiN substrate using the same process conditions described in Example 6 (eg, using RuCp*DMDEP/oxygen at 300 ° C) and using atomic force microscopy (AFM). )analysis. The tantalum film covering the area of 1.00 μm x 1.00 μm x 6.32 nm was found to have a low surface roughness or an RMS of 0.31 nm as measured by AFM.

Claims (6)

A composition comprising one or more compounds selected from the group consisting of dihydropyrazinyl and dihydropyrazine metal complexes having the following formulas 3A to 3H: Wherein each of the formulae 3A to 3C, R ¹ , R ² , R ³ , R ⁴ are each independently selected from a C ₁ -C ₆ linear, branched or cyclic alkyl group; and the R ⁵ is independently selected from a hydrogen atom. And a C ₁ -C ₆ linear, branched or cyclic alkyl group; (L) is an anion selected from the group consisting of cyclopentadienyl, pentaalkylcyclopentadienyl, pentamethylpentadienyl, and dimethyl Pentadienyl, trimethylpentadienyl, methylpentadienyl, ethylpentadienyl, imidazolyl, trialkylimidazolyl, pyrrolyl and alkylpyrrolyl; M-based divalent metals ;x=1 or 2; x+y=2; X is independently selected from a hydrogen atom, a C ₁ -C ₆ linear, branched or cyclic alkyl group, and SiR ⁶ , and wherein R ⁶ is independently selected from C ₁ -C ₃ linear or branched alkyl; Wherein R ¹ , R ² , R ³ , R ⁴ are each independently selected from C ₁ -C ₆ linear, branched or cyclic alkyl groups; R ⁵ is independently selected from hydrogen atoms and C ₁ -C ₆ linear, branched or cyclic alkyl; (L) is an anion selected from the group consisting of cyclopentadienyl, pentaalkylcyclopentadienyl, pentamethylpentadienyl, dimethylpentadienyl , trimethylpentadienyl, methylpentadienyl, ethylpentadienyl, imidazolyl, trialkylimidazolyl, pyrrolyl and alkylpyrrolyl; M system monovalent metal; x=1; y =1; and the Z system is independently selected from the group consisting of a hydrogen atom, a C ₁ -C ₆ linear, branched or cyclic alkyl group, and SiR ⁶ , wherein R ⁶ is independently selected from linear or branched C ₁ -C ₃ alkyl; Wherein R ¹ , R ² , R ³ , R ⁴ are each independently selected from a C ₁ -C ₆ linear, branched or cyclic alkyl group; R ⁵ is selected from a hydrogen atom and a C ₁ -C ₆ linear , branched or cyclic alkyl group; (Q) is selected from benzene and alkyl benzenes; M based metal; x = 1 or 2; y = 1; and Z are independently selected hydrogen atom, C ₁ -C ₆ a linear, branched or cyclic alkyl group and SiR ⁶ wherein R ⁶ is a C ₁ -C ₃ linear or branched alkyl group; Wherein each of the formulae 3F to 3H, R ¹ , R ² , R ³ , R ⁴ are each independently selected from a C ₁ -C ₆ linear, branched or cyclic alkyl group; and the R ⁵ is independently selected from a hydrogen atom. And a C ₁ -C ₆ linear, branched or cyclic alkyl group; (Q) is a neutral ligand; M is a monovalent metal; y = 1; the X is independently selected from a hydrogen atom, C ₁ -C ₆ linear, Branched or cyclic alkyl and SiR ⁶ , and wherein R ⁶ is independently selected from C ₁ -C ₃ linear or branched alkyl. The composition of claim 1, wherein the metal complex does not contain an oxygen atom. The composition of claim 1, wherein the dihydropyrazine ligand is 2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine or the dihydrogen The pypyrazinyl ligand 2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazinyl. The composition of claim 1, wherein the metal is ruthenium or cobalt. The composition of any one of the preceding claims, wherein L is pentamethylcyclopentadienyl (Cp*). The composition of claim 1, wherein the metal complex comprises at least one selected from the group consisting of (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl -5,6-diethylpyrazinyl)anthracene, (pentamethylcyclopentadienyl) (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine) Cobalt, (2,2-dihydro-3,3-dimethyl-5,6-diethylpyrazine)(phenyl)anthracene and combinations thereof.